Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
  • C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
  • H01L23/293—Organic, e.g. plastic
  • H01L23/296—Organo-silicon compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
  • H01L2924/0001—Technical content checked by a classifier
  • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
  • H01L33/52—Encapsulations
  • H01L33/56—Materials, e.g. epoxy or silicone resin

Definitions

• the present invention relates to a novel organosilicon compound, a thermosetting resin composition containing the compound and useful for applications such as optical materials and electrical insulating materials, a cured product obtained by thermosetting the composition, and an optical semiconductor using the same
• the present invention relates to a sealing material.
• light emitting devices such as light emitting diodes (LEDs) have been put to practical use in various display boards, image reading light sources, traffic signals, large display units, mobile phone backlights, and the like.
• These light emitting devices are generally sealed with a curable resin obtained by curing an aromatic epoxy resin and an alicyclic acid anhydride as a curing agent.
• a curable resin obtained by curing an aromatic epoxy resin and an alicyclic acid anhydride as a curing agent.
• the alicyclic acid anhydride is easily discolored by an acid and that it takes a long time to cure.
• the sealed curable resin is yellowed.
• Patent Documents 1 and 2 a method of sealing an LED or the like with a curable resin using an alicyclic epoxy resin or an acrylic resin and a cationic polymerization initiator has been attempted (Patent Documents 1 and 2). See).
• the cation-polymerized curable resin is very fragile and has a defect that it is liable to cause crack fracture in a cold cycle test (also referred to as a heat cycle test).
• this curable resin has a defect that the sealed curable resin is markedly colored after curing, as compared with a curable resin using a conventional aromatic epoxy resin and acid anhydride. Therefore, this curable resin is not suitable for applications requiring colorless transparency, particularly for LED sealing applications requiring heat resistance and transparency.
• cured products using silicone resins such as methyl silicone resin and phenyl silicone resin have poor adhesion to polyamide resin used for LED substrates and silver used for electrodes compared to epoxy resins, and peeled off due to heat shock, etc. There was a drawback that it was easy to produce.
• Methyl silicone resins and phenyl silicone resins mainly have polysilsesquioxane compounds having a branched structure as a result of hydrolysis and condensation reaction of alkoxysilane monomers, but these have residual silanol groups, so heat shock There is a problem that the physical properties change due to, for example, the hardness changing over time. For example, when exposed to high temperature conditions such as a reflow process, there is a drawback that cracks are likely to occur due to an increase in hardness.
• Patent Documents 4 to 8 disclose a cage-type silicon compound and a polymer thereof, and describe that heat resistance is good.
• This is a cage-type silsesquioxane called a double-decker with a controlled structure, unlike the polysilsesquioxane with a random structure usually obtained from the hydrolysis and condensation reaction of alkoxylane. is there.
• this product does not have a silanol group that hinders storage stability and hardness increase due to secondary curing after heat curing, so it is suitable for applications that require long-term reliability such as LED encapsulants. It is thought that. However, these are all solid or crystalline. Since a solvent is required for molding for practical use, it cannot be used as it is for an LED or the like.
• Patent Document 9 discloses a composition for a sealant containing a cage silicon compound and a sealant.
• a thermosetting polymer is obtained by hydrosilylation reaction between a cage-type silicon compound having a SiH group and a compound having a vinyl group, and this is further hydrosilylated and cured with a compound having a vinyl group.
• a cured product is disclosed.
• the description of Patent Document 9 is not clear, and a cured product cannot be obtained by the method described in Patent Document 9.
• JP 61-112334 A Japanese Patent Laid-Open No. 02-289611 JP 2003-277473 A JP 2006-070049 A International Publication No. 2004/081084 Pamphlet JP 2004-331647 A International Publication No. 2003/24870 Pamphlet International Publication No. 2004/24741 Pamphlet JP 2007-45971 A
• An object of the present invention is to provide a silicone resin-based thermosetting resin composition capable of obtaining a cured product having a high refractive index and good heat resistance. It is another object of the present invention to provide a silicone resin-based thermosetting resin having improved adhesion to a thermoplastic resin such as a polyamide resin used for an LED substrate and a metal such as silver used for an electrode. Another object is to provide a silicone resin-based thermosetting resin composition that hardly changes in physical properties due to increased hardness and has excellent crack resistance.
• the viscosity of the curable composition containing the thermosetting resin composition is from 10 Pa ⁇ s to 10 Pa ⁇ s, which is suitable for the mold method, from the optimum viscosity range of 1 Pa ⁇ s to 10 Pa ⁇ s suitable for the dispenser method that is an LED sealing method.
• One object is to provide a novel organosilicon compound to be contained in the thermosetting resin composition, a cured product comprising the thermosetting silicone resin composition, a molded body, and a light sealing material for a light emitting diode. .
• the present inventors have intensively studied to solve the above problems. As a result, we have succeeded in synthesizing a novel liquid organosilicon compound containing a cage-type silicon compound structure. Since the organosilicon compound is liquid, it does not require a solvent, and a cured product obtained from a thermosetting resin composition containing the organosilicon compound and a curing agent has excellent adhesion to polyamide resin and silver. In addition, the present inventors have found that it is excellent in refractive index, transparency, heat resistance, heat yellowing resistance, etc., has little change in physical properties due to an increase in hardness, and has excellent crack resistance, thereby completing the present invention. That is, the present invention has the following configuration.
• a liquid organosilicon compound represented by the following general formula (1) is independently a group represented by the following formula (I), formula (II) or formula (III), per molecule of the liquid organosilicon compound represented by the general formula (1) (the compound Is a mixture of compounds in which the ratio of the group represented by the formula (I), the group represented by the formula (II) and the group represented by the formula (III) is different, the compound (one molecule average)
• a is the number of groups represented by formula (II)
• b is the number of groups represented by formula (II)
• R 1 is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and R 2 and R 3 are each independently alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and A group selected from phenyl, m and n are the number of repetitions of —OSi (R 3 ) 2 —, and are average values satisfying 1 to 50;
• thermosetting resin composition containing the liquid organosilicon compound according to [1].
• thermosetting resin composition according to [3] further comprising a liquid organosilicon compound obtained from the structural unit represented by C and the structural unit represented by D in Formula (3).
• R 1 is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl
• R 2 and R 3 are each independently having 1 to 4 carbon atoms.
• thermosetting resin composition according to [3] or [4] further comprising a platinum catalyst.
• thermosetting resin composition obtained by molding the cured product according to [7].
• a coating film obtained by applying the thermosetting resin composition according to any one of [3] to [6].
• a resin encapsulant for optical semiconductors comprising the thermosetting resin composition according to any one of [3] to [6].
• the cured product of the thermosetting resin composition of the present invention is excellent in, for example, high refractive index, transparency, heat resistance, heat yellowing resistance and the like. Therefore, the molded body made of a cured product can be suitably used for applications such as a semiconductor sealing material, an optical semiconductor sealing material, an optical semiconductor die bond material, an insulating film, a sealant, and an optical lens.
• transparent materials, optical materials, optical films, optical sheets, adhesives, electronic materials, insulating materials, interlayer insulating films, paints, inks, coating materials, molding materials, potting materials, liquid crystal sealants, display device sealants, Solar cell sealing material, resist material, color filter, electronic paper material, hologram material, solar cell material, fuel cell material, display material, recording material, waterproof material, moisture proof material, battery solid electrolyte, gas separation can be used for membranes. Moreover, it can use for the additive etc. to other resin.
• Organosilicon compound of the present invention is represented by the following general formula (1).
• R 1 is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl
• R 2 and R 3 are each independently alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and A group selected from phenyl, m and n are the number of repetitions of —OSi (R 3 ) 2 —, and are average values satisfying 1 to 50;
• a and b are a mixture of compounds in which the ratio of the group represented by the formula (I) and the group represented by the formula (II) is different per molecule of the liquid organosilicon compound represented by the general formula (1) In some cases, this is also the number of SiH groups and the number of vinyl groups of the compound per molecule).
• a is 0 to 3.5 (b + 2c is 0.5 to 4.0)
• a liquid organosilicon compound can be obtained.
• a is larger than 3.5 (b + 2c is smaller than 0.5)
• a large amount of the above formula (2-1) which is a solid not involved in the reaction is contained, and it cannot be dissolved and precipitates and does not become liquid.
• C is the number of components that crosslink the molecules of the liquid organosilicon compound represented by the general formula (1). That is, since it does not contain SiH groups or vinyl groups, it does not contribute to the ratio of SiH groups or vinyl groups. Further, by increasing this component, the amount of the component (2-1) that is relatively solid can be reduced, so that it is easy to obtain a liquid organosilicon compound.
• organosilicon compound of the present invention represented by the general formula (1) has on average more SiH groups than vinyl groups and is defined as a so-called SiH group type thermosetting resin.
• the polymer can be defined as a so-called vinyl group type polymer.
• a is preferably 1.0 to 3.0 from the viewpoint of remarkably exhibiting excellent characteristics when a cured product is used. More preferably, it is 5 to 2.5.
• the compound has a relatively low viscosity.
• the crosslinking component increases and the viscosity of the compound increases.
• the cross-linking of molecules is in a very advanced state, and the liquid state cannot be maintained because it becomes a gel.
• the organosilicon compound of the present invention is, for example, a diorganopolysiloxane having a silsesquioxane derivative represented by the following general formula (2-1) and a vinyl group at both ends represented by the following general formula (2-2). It can be obtained by subjecting siloxane to a hydrosilylation reaction at a reaction molar ratio of 2 or more.
• each R 1 is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl.
• R 2 and R 3 are Each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl.
• R 1 , R 2 and R 3 are preferably methyl, ethyl and propyl, more preferably methyl.
• n is the number of repetitions of —OSi (R 3 ) 2 —, and is an average value satisfying 1 to 50.
• the structure of the organosilicon compound represented by the formula (1) of the present invention is controlled by suppressing the crosslinking reaction in order to make it liquid. Specifically, the reaction is performed with the number of moles of the general formula (2-2) in the general formula (2-1) being twice or more. That is, one end of the diorganopolysiloxane compound having a vinyl group at the terminal represented by the general formula (2-2), partially or all of the four SiH groups in the general formula (2-1). Thus, an organosilicon compound having a desired SiH group: vinyl group ratio can be obtained.
• the above general formula (2-1) is a solid, but a liquid organosilicon compound can be obtained by bonding a flexible polysiloxane chain with a high degree of freedom.
• reaction molar ratio is in the range of 1 or more and less than 2, a crosslinking reaction is likely to occur, that is, the hydrosilylation reaction between the produced monomers proceeds and a high-viscosity liquid or further gelation occurs, so that it does not become liquid.
• a suitable amount of diorganopolysiloxane having a vinyl group at the terminal represented by the general formula (2-2) can be reacted.
• the crosslinking reaction of the general formula (2-1) proceeds, and the amount of the general formula (2-1) that is a solid in the compound can be reduced.
• the amount of the general formula (2-2) is 1 or less with respect to 1 mole of the general formula (2-1).
• the hydrosilylation reaction of the compounds (2-1) and (2-2) can be performed by a known method, and can be performed in a solvent or in the absence of a solvent.
• the solvent used for the hydrosilylation reaction is not particularly limited as long as it does not inhibit the progress of the reaction.
• Preferred solvents are hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran (THF) and dioxane, methylene chloride and tetrachloride.
• Halogenated hydrocarbon solvents such as carbon and ester solvents such as ethyl acetate. These solvents may be used alone or in combination. Among these solvents, aromatic hydrocarbon solvents, and toluene is most preferable.
• the hydrosilylation reaction can be carried out at room temperature (25 ° C.) and normal pressure (1 atm), but is preferably heated to promote the reaction.
• the reaction When the reaction is carried out in the absence of a solvent, the above compounds (2-1) and (2-2), which are raw materials, must be reacted in a homogeneous system. preferable.
• the reaction When no reaction solvent is used, the reaction may be performed at a temperature equal to or higher than the temperature at which all raw materials become homogeneous.
• the amount of hydrosilylation catalyst to be used is limited, so that the temperature is 80 ° C. or higher.
• the heating is preferably performed at a temperature of 100 ° C. or higher, more preferably in the range of 110 ° C. to 150 ° C.
• the reaction can be allowed to proceed more easily by adding a hydrosilylation catalyst.
• a hydrosilylation catalyst examples include Karstedt catalyst, Spear catalyst, hexachloroplatinic acid and the like, which are generally well known catalysts.
• the addition amount of the hydrosilylation catalyst will be described. Since these hydrosilylation catalysts have high reactivity, the reaction can proceed sufficiently if added in a small amount, but the preferred catalyst concentration range varies depending on the organosilicon compound satisfying the ranges of a, b, and c.
• the value of a decreases as hydrosilylation proceeds during the reaction. That is, when it is desired to reduce the value of a, that is, when the reaction is to proceed sufficiently, the catalyst concentration may be increased. On the other hand, when it is desired to increase the concentration, that is, when the reaction is not desired to proceed so much, the catalyst concentration may be lowered.
• the amount of Pt is preferably in a concentration range of 0.001 to 0.08 ppm with respect to the compound represented by the formula (2-1). More specifically, the concentration range of 0.001 to 0.04 ppm is more preferable in the range of 1.5 ⁇ a ⁇ 3.5, and 0 in the range of 0.8 ⁇ a ⁇ 1.5. A concentration range of .04 ppm to 0.1 ppm is preferred. Within these ranges, the organosilicon compound of the present invention is easy to control the reaction, has no thickening in the post-treatment step, and has good storage stability at room temperature.
• the amount of Pt is preferably in the range of 0.1 ppm to 5 ppm with respect to the compound represented by the formula (2-1).
• the removal method of the unreacted vinyl silicone which is the solvent used in the reaction and the unreacted raw material compound will be described.
• the unreacted vinyl silicone here means an unreacted portion which did not contribute to the reaction among the diorganopolysiloxane having vinyl groups at both ends used in the hydrosilylation reaction.
• Volatile vinyl silicone can be removed by distillation.
• vinyl silicone having a high boiling point or non-volatility can be removed by a solvent extraction method using a difference in distribution to a solvent.
• vinyl silicone since vinyl silicone has two or more functional groups, it may be optionally left as it is and used as a thermosetting resin composition.
• the organosilicon compound of 0.8 ⁇ a ⁇ 3.5 of the present invention has both SiH groups and vinyl groups, so that hydrosilylation reaction does not proceed during distillation. You need to be careful.
• a thermal history is unavoidable, such as a simple distillation operation, it is desirable to distill at a temperature below the reaction temperature.
• a preferable temperature at the time of removing excess vinyl silicone in the simple distillation operation is 60 to 100 ° C., more preferably 70 to 90 ° C. If this temperature is exceeded, the hydrosilylation reaction proceeds during distillation, and it may not be possible to obtain a desired vinyl group and SiH group ratio.
• the distillation may be carried out by adding a curing retarder that delays the progress of the hydrosilylation reaction so that the hydrosilylation reaction does not proceed during the distillation.
• a distillation method using a thin film distillation apparatus may be used.
• the distillation temperature may be higher than the reaction temperature because there is no fear that the hydrosilylation reaction proceeds due to thermal history.
• diorganopolysiloxane having vinyl groups at both ends having a high boiling point is used in the reaction and it is desired to remove this excess.
• the upper limit of the temperature is not particularly defined, but is preferably in the range of 120 ° C to 180 ° C.
• removal of low-volatility vinyl silicone can be achieved by a solvent washing method utilizing the difference in distribution to the solvent.
• a preferred solvent for dissolving vinyl silicone is a solvent having a large dissolving power and a relatively low boiling point.
• a preferred washing solvent is a lower alcohol.
• a particularly preferred cleaning solvent is methanol.
• the organosilicon compound of the present invention is characterized by being liquid.
• Conventionally known organosilicon compounds and their polymers are in a solid state or a crystalline state. After being dissolved in a solvent to enable easy molding, a coating film is formed by coating and poured into a mold. It was necessary to make a molded body.
• the organosilicon compound of the present invention does not need to be dissolved in a solvent and can be easily molded, it is excellent in handling properties because it is a liquid with good fluidity even at room temperature.
• this compound is used as a thermosetting resin composition, the cured product is excellent in transparency, heat resistance, and adhesiveness.
• the organosilicon compound of the present invention is not only excellent in adhesion to polyamide resin and silver, but also a cured product prepared by curing a composition containing the compound, as well as refractive index, transparency, and heat resistance. It is excellent in heat-resistant yellowing and the like, and is an excellent material for cured products in which the defects of cured products made of silicone resins such as phenyl silicone resin and methyl silicone resin that have been conventionally used are improved.
• the refractive index of the cured product is 1.4 or more, it can be used without any problem, preferably 1.50 or more, and the upper limit is not particularly limited.
• the silsesquioxane derivative represented by the general formula (2-1) can be synthesized, for example, by the method disclosed in International Publication No. 2004/024741 pamphlet. Examples of the compound represented by the general formula (2-1) (hereinafter referred to as “DD-4H”) are shown below.
• the diorganopolysiloxane having vinyl groups at both ends represented by the general formula (2-2) can be synthesized by a known method, or a commercially available compound may be used.
• the compound represented by the general formula (2-2) can be produced using, for example, 1,5-divinylhexamethyltrisiloxane (hereinafter referred to as “DVTS”) represented by the following structure. it can.
• DVTS 1,5-divinylhexamethyltrisiloxane
• Other examples include 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane.
• the value of n in the general formula is 1 to 50, preferably 2 to 30, and more preferably 2 to 20.
• n in the above general formula can be adjusted by appropriately selecting the molar ratio of the raw materials for synthesis (for example, 1,3-divinyltetramethyldisiloxane and octamethylcyclotetrasiloxane).
• thermosetting resin composition of the present invention is a liquid organosilicon compound represented by the above general formula (1), or a compound represented by the above general formula (2-1) and the above general formula (2-2). It is a thermosetting resin composition containing a liquid organosilicon compound obtained by hydrosilylation reaction of the represented compound. A cured product is obtained by adding a curing catalyst to the thermosetting resin composition and heating the composition.
• thermosetting resin composition further includes a diorganopolysiloxane having two or more vinyl groups. It is also a preferable aspect to further contain a silicon compound.
• the silicon compound having two or more vinyl groups is not particularly limited as long as it is a silicon compound having two or more vinyl groups for crosslinking.
• a linear polysiloxane having vinyl groups at both ends can be used. . Specific examples include linear polysiloxanes having vinyl groups at both ends such as DVTS.
• the silicon compound having two or more vinyl groups may be used alone or in a blend of two or more different compounds.
• the content ratio of the total SiH groups and the total vinyl groups is preferably 1: 2 to 2: 1 in terms of the functional group molar ratio of SiH groups to vinyl groups.
• thermosetting resin composition of the present invention further comprises the following general formula (3): It is also a preferred embodiment to contain an organosilicon compound having a SiH group represented by: This compound is a polymer composed of a structural unit C and a structural unit D, and a preferred molecular weight range is 3,000 to 100,000 in terms of weight average molecular weight.
• R 1 is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl
• R 2 and R 3 are each independently having 1 to 4 carbon atoms.
• R 1 , R 2 and R 3 are preferably methyl, ethyl and propyl, more preferably methyl.
• n is the number of repetitions of —OSi (R 3 ) 2 — and is an average value satisfying 2 to 50.
• the mole fraction of the structural unit represented by C in the liquid organosilicon compound is ⁇ and the mole fraction of the structural unit represented by D in the liquid organosilicon compound is ⁇ , ⁇ and The ratio of n ⁇ ⁇ ( ⁇ : n ⁇ ⁇ ) satisfies 1: 3 to 1: 100.
• This compound is, for example, a reaction mole of a diorganopolysiloxane having vinyl groups at both ends represented by the general formula (2-2) with respect to the silsesquioxane derivative represented by the general formula (2-1). It can be obtained by hydrosilylation reaction at a ratio of 0.75.
• the content ratio of the total SiH groups and the total vinyl groups is preferably 1: 2 to 2: 1 in terms of the functional group molar ratio of SiH groups to vinyl groups.
• the curing catalyst is not particularly limited as long as it is a transition metal catalyst usually used as a reaction catalyst, but a platinum catalyst is preferably used.
• a platinum catalyst is preferably used.
• a normal hydrosilylation catalyst can be selected.
• preferred hydrosilylation catalysts are Karstedt catalyst, Speyer catalyst, hexachloroplatinic acid and the like, which are generally well-known platinum catalysts.
• the amount used is 0.1 ppm to 10 ppm in terms of the weight ratio of the transition metal contained in the catalyst to the thermosetting resin composition. If the addition ratio is in the above range, curing failure is unlikely to occur, the pot life after preparation of the thermosetting resin composition is too short, and there is no risk of inconvenience that it cannot be used, and coloring of the cured product does not occur. .
• a preferable addition ratio is 0.5 ppm to 4 ppm.
• thermosetting resin composition of the present invention can be used without using a solvent.
• polysilsesquioxane is in a solid state, but the organosilicon compound represented by the general formula (1) of the present invention is in a liquid state. That is, the composition of the present invention is also liquid. Therefore, since it can be used for an application in which mixing of a solvent is not preferred, the range of applications is greatly expanded.
• thermosetting resin composition of the present invention may further contain the following components.
• Powdery reinforcing agents and fillers for example, metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, transparent fillers such as glass beads, aluminum hydroxide and the like Metal hydroxide, kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc. These are mix
• a desirable ratio when these are blended is in a range of 0.1 to 0.9 as a weight ratio with respect to the total amount of the thermosetting resin composition of the present invention.
• a preferred ratio when the above components (v) to (vi) are blended is 0.01 to 0.50 in terms of a weight ratio with respect to the total amount of the thermosetting resin composition.
• (Vii) Phenol-based, sulfur-based and phosphorus-based antioxidants.
• a preferred ratio when using the curing accelerator is in the range of 0.0001 to 0.1 as a weight ratio with respect to the total amount of the thermosetting resin composition of the present invention.
• An ultraviolet absorber for improving light resistance A preferred ratio when using the curing accelerator is in the range of 0.0001 to 0.1 as a weight ratio with respect to the total amount of the thermosetting resin composition of the present invention.
• thermosetting resin composition of the present invention can be produced, for example, by the following method.
• the organosilicon compound of the present invention, the curing catalyst, and, if necessary, the above optional components are stirred and mixed, and then degassed under reduced pressure.
• the mixture can be poured into a mold, heated at 80 ° C. for 1 hour, and finally heated at 150 ° C. for 1 to 5 hours to be cured.
• the transparency of the cured product is determined by measuring the transmittance of the cured product before and after the heat resistance test with an ultraviolet-visible spectrophotometer and evaluating the transmittance of the light transmittance at 400 nm when the transmittance of the light transmittance at 180 ° C. Is preferably 90% or more. When each value falls within these ranges, it indicates that the cured product is colorless and highly transparent, and is particularly preferably used in fields such as optical semiconductor encapsulants that require transparency. it can.
• the cured product obtained by thermosetting the thermosetting resin composition of the present invention has very good heat-resistant transparency due to the structure of the silsesquioxane derivative represented by the general formula (2-1). Is attributed. That is, the absence of a silanol group in the skeleton of the double-decker silsesquioxane provides a property excellent in heat-resistant transparency and hardly causes physical changes such as increase in hardness due to heat over time.
• thermosetting the thermosetting resin composition of the present invention is molded into a molded body, which can be used for various applications.
• the composition has a light emitting function and can be used as an LED composition.
• an optical semiconductor sealing material, a semiconductor sealing material, a die bond material for an optical semiconductor, an insulating film, a sealing material, an adhesive, an optical lens, and the like can be given.
• DVDS (1,3-divinyltetramethyldisiloxane): DVEST manufactured by GELEST (1,5-divinylhexamethyltrisiloxane): diphenyldimethoxysilane manufactured by GELEST: manufactured by GELEST
• a reaction vessel equipped with a reflux condenser, a thermometer, and a dropping funnel was charged with 2,005 g of cyclopentyl methyl ether, 243 g of 2-propanol, 1,400 g of ion-exchanged water, and 461 g of hydrochloric acid at room temperature under a nitrogen atmosphere.
• 800 g of the above-obtained compound (DD-ONa) and 2,003 g of cyclopentyl methyl ether were charged into a dropping funnel and dropped into a reactor over 30 minutes, and stirring was continued for 30 minutes after completion of the dropping. .
• a reactor equipped with a dropping funnel, a thermometer, and a reflux condenser was charged with 7,160 g of the compound (DD-4OH) obtained above, 72,600 g of toluene, and 2,850 g of dimethylchlorosilane, and dried nitrogen. And sealed.
• 3,230 g of triethylamine was dropped from the dropping funnel in about 20 minutes. At this time, the dropping speed was adjusted so that the solution temperature was 35 ° C. to 40 ° C. After completion of the dropping, stirring was continued for 1 hour to complete the reaction.
• the filtrate was transferred to an eggplant flask, and after evaporation of low-boiling components under reduced pressure conditions of 80 ° C. and 10 mmHg using an evaporator, 314 g of a colorless transparent liquid (diorganopolysiloxane 1) was obtained.
• Si-NMR was measured, and from the ratio of the integrated intensity of the Si peak at the molecular chain end to the Si peak inside the molecular chain, n (average value) in the following formula was 3.9, and the vinyl group equivalent was 188 g / calculated as mol.
• Synthesis Examples 3-5 Diorganopolysiloxanes 2 to 4 were prepared in the same manner as in Synthesis Example 2, except for the amount of 1,3-divinyltetramethyldisiloxane (DVDS) and octamethylcyclotetrasiloxane (D4) charged, and the distillation conditions of the low boiling point.
• DVDS 1,3-divinyltetramethyldisiloxane
• D4 octamethylcyclotetrasiloxane
• Table 1 shows n (average value) and vinyl equivalent of diorganopolysiloxanes 1 to 4.
• the obtained reaction liquid was transferred to an eggplant flask, and toluene was distilled off under reduced pressure at 100 ° C. and 5 mmHg with an evaporator.
• the obtained viscous liquid was dissolved in 350 g of acetone, 1.7 g of activated carbon was added, and the mixture was stirred for 5 hours.
• Activated carbon was filtered under reduced pressure using a 0.2 ⁇ l filter. The filtrate was again evaporated with an evaporator under reduced pressure at 70 ° C.
• Example 1 Compound (1-1) was produced by the following reaction. 50 g (0.0384 mol) of the silsesquioxane derivative (DD-4H) produced in Synthesis Example 1 and 51.3 g of DVTS in a 200-mL reaction vessel equipped with a thermometer, a reflux condenser, and a stirrer (0.197 mol) (5-fold mol with respect to DD-4H), and 37.5 g of toluene was added as a solvent. Heating and stirring were started under a nitrogen atmosphere. After the contents reached 115 ° C., the Calsted catalyst was added so that the Pt concentration was 0.004 ppm with respect to DD-4H, and the mixture was heated and stirred.
• DD-4H silsesquioxane derivative
• the reaction was monitored by GPC, and the reaction was stopped by stopping the heating after 7 hours.
• the reaction solution was transferred to an eggplant flask and toluene and excess DVTS were distilled off under reduced pressure at 70 ° C. and 1 mmHg by an evaporator to obtain 58 g of a colorless and transparent liquid having a viscosity of 95 Pa ⁇ s at 25 ° C.
• Mn 1200
• Example 2 25 g (0.0192 mol) of the silsesquioxane derivative (DD-4H) produced in Synthesis Example 1 and 51.3 g (0.197 mol) of DVTS (10.3 times mol of DD-4H), The reaction was performed in the same manner as in Example 1 except that toluene was changed to 25 g as a solvent and the Pt concentration was changed to 0.016 ppm with respect to DD-4H. The reaction was traced by GPC, and the post-treatment was performed in the same manner as in Example 1 except that the heating was stopped after 12 hours to obtain 33 g of a colorless transparent liquid having a viscosity of 20 Pa ⁇ s at 25 ° C.
• Example 3 270 g (0.207 mol) of the silsesquioxane derivative (DD-4H) produced in Synthesis Example 1 and 276 g (1.062 mol) of DVTS (5.1 times mol with respect to DD-4H) as a solvent The reaction was performed in the same manner as in Example 1 except that toluene was changed to 202 g. The reaction was traced by GPC. After 7 hours, the heating was stopped and the mixture was cooled to 70 ° C. Then, using a single distillation apparatus, toluene and excess DVTS were distilled off under reduced pressure conditions of 70 ° C and 5 mmHg.
• Example 4 250 g (0.192 mol) of the silsesquioxane derivative (DD-4H) produced in Synthesis Example 1 and 512.6 g (1.972 mol) of DVTS (10.3 times mol to DD-4H), The reaction was performed in the same manner as in Example 1 except that the toluene was changed to 250 g and the Pt concentration was changed to 0.08 ppm with respect to DD-4H. The reaction was traced by GPC, and the post-treatment was performed in the same manner as in Example 1 except that the heating was stopped after 12 hours to obtain 332 g of a colorless and transparent liquid having a viscosity at 25 ° C. of 14 Pa ⁇ s.
• Example 5 25 g (0.0192 mol) of the silsesquioxane derivative (DD-4H) produced in Synthesis Example 1 and 51.26 g (0.197 mol) of DVTS (10.3 times mol of DD-4H), The reaction was performed in the same manner as in Example 1 except that the Calsted catalyst was changed to 2 ppm with respect to DD-4H and the reaction temperature was changed to 150 ° C. After confirming the disappearance of all SiH groups by IR, the reaction was stopped, excess DVTS was removed with an evaporator at 100 ° C. and 1 mmHg, and the viscosity at 25 ° C. was 7.5 Pa ⁇ s. 35 g of a clear liquid was obtained.
• Example 6 50 g (0.0394 mol) of the silsesquioxane derivative (DD-4H) produced in Synthesis Example 1 and 31.1 g (0.0827) of diorganopolysiloxane 2 having vinyl groups at both ends described in Table 1 Mol) (2.1 mol per mol of DD-4H), 18.7 g of toluene as a solvent, and the Pt concentration was changed to 0.004 ppm with respect to DD-4H. The reaction was performed. The reaction was traced by GPC, and after 6 hours, except that heating was stopped, post-treatment was performed in the same manner as in Example 1 to obtain 75 g of a colorless transparent liquid having a viscosity at 25 ° C.
• Example 7 25 g (0.0197 mol) of the silsesquioxane derivative (DD-4H) produced in Synthesis Example 1 and 18.9 g (0.042 mol) of diorganopolysiloxane 3 having vinyl groups at both ends shown in Table 1. Mol) (2.1 times mol with respect to DD-4H), 18.7 g of toluene as a solvent, and the Pt concentration was changed to 0.004 ppm with respect to DD-4H, as in Example 1. Reaction was performed. The reaction was traced by GPC, and the reaction was stopped by stopping the heating after 3 hours, and toluene was distilled off from the reaction solution at 70 ° C. under a reduced pressure of 1 mmHg with an evaporator.
• Example 8 25 g (0.0197 mol) of the double-decker silsesquioxane derivative (DD-4H) produced in Synthesis Example 1 and diorganopolysiloxane 4 having vinyl groups at both ends shown in Table 1 (FM-2205) 56.8 g (0.0789 mol) (4 times mol with respect to DD-4H), 10 g of toluene as a solvent, and the Pt concentration was changed to 1 ppm with respect to DD-4H. went. The reaction temperature was changed to 120 ° C. for 12 hours and further to 140 ° C. for 6 hours, and after all SiH had disappeared, toluene was distilled off under reduced pressure conditions of 120 ° C.
• Example 9 Diorganopolysiloxane having 2 g (0.0015 mol) of the silsesquioxane derivative (DD-4H) produced in Synthesis Example 1, a partly phenyl group in the side chain, and a vinyl group at both ends ( The same as Example 1 except that Synthesis Example 6) was changed to 25.5 g (0.0067 mol) (4.5 times mol to DD-4H) and the Pt concentration was changed to 0.04 ppm with respect to DD-4H. The reaction was performed in the same manner.
• DD-4H silsesquioxane derivative
• the reaction was traced by GPC, and the post-treatment was performed in the same manner as in Example 1 except that the heating was stopped after 12 hours to obtain 26 g of a colorless and transparent liquid having a viscosity at 25 ° C. of 0.6 Pa ⁇ s. Unreacted vinyl silicone was left as it was as a thermosetting resin component.
• Mn 1400
• Mw 6700
• Example 10 300 g (0.230 mol) of the double-decker silsesquioxane derivative (DD-4H) produced in Synthesis Example 1 and 52.2 g of diorganopolysiloxane 4 having vinyl groups at both ends shown in Table 1 ( 0.073 mol) (0.32 times mol with respect to DD-4H), 304 g of toluene was added as a solvent, and the mixture was heated to 120 ° C. to dissolve the raw materials.
• Pt concentration was added so as to be 0.006 ppm with respect to DD-4H. This reaction solution was reacted by heating and stirring at 120 ° C. for 16 hours.
• Example 11 50 g (0.0384 mol) of the double-decker silsesquioxane derivative (DD-4H) produced in Synthesis Example 1 and 18.0 g of diorganopolysiloxane 5 having vinyl groups at both ends shown in Table 1 ( 0.02 mol) (0.52 mol with respect to DD-4H), 50 g of toluene was added as a solvent, and the mixture was heated to 120 ° C. to dissolve the raw materials.
• Pt concentration was added so as to be 0.006 ppm with respect to DD-4H. This reaction solution was reacted by heating and stirring at 120 ° C. for 5 hours.
• Example 12 50 g (0.0384 mol) of the double-decker silsesquioxane derivative (DD-4H) produced in Synthesis Example 1 and 13.8 g of diorganopolysiloxane 4 having vinyl groups at both ends shown in Table 1 ( 0.0192 mol) (0.5 times mol with respect to DD-4H), 50 g of toluene was added as a solvent, and the mixture was heated to 120 ° C. to dissolve the raw materials.
• Pt concentration was added so as to be 0.006 ppm with respect to DD-4H. This reaction solution was reacted by heating and stirring at 120 ° C. for 4 hours.
• Tables 2 and 3 summarize the reaction conditions, obtained structures, viscosities, and the like for the compounds synthesized in Examples 1 to 9 and Comparative Synthesis Example 1.
• thermosetting resin composition 14 Comparative cured product example 1 Further, 1.64 g of the silsesquioxane polymer obtained in Comparative Synthesis Example 2 and 1 g of divinyltetramethyldisiloxane were mixed, and this was used as a thermosetting resin composition 14. Table 4 shows the blending amount (g) of the thermosetting resin composition 14. After the thermosetting resin composition 14 was poured into a glass mold, it was heated at 100 ° C. for 30 minutes and subsequently heated at 200 ° C. for 3 hours, but it was not cured at all.
• thermosetting resin composition A mixture of the compound synthesized in the above example and DVTS or the polyorganosiloxane synthesized in the above synthesis example was placed in a screw tube.
• the screw tube was set in a rotating / revolving mixer ("Awatori Nerita (registered trademark)" ARE-250 manufactured by Shinky Corporation), and mixed and defoamed.
• Silane coupling agent concentration of S510 (3-glycidoxypropyltrimethoxysilane: manufactured by Chisso Corporation) is 0.025 wt%
• curing retarder MVS-H (1,3,5,7-tetravinyl-1 , 3,5,7-tetramethylcyclotetrasiloxane (manufactured by Chisso Corporation) so that the concentration is 10 ppm and the concentration of the platinum catalyst is 1 ppm.
• Resin compositions 1 to 12 were obtained.
• Table 4 shows the blending amount (g) of each thermosetting resin composition.
• Table 5 shows the viscosity of the thermosetting resin composition obtained by blending and mixing the thermosetting resin composition as shown in Table 4, and the refractive index and hardness of the cured product obtained by curing the composition. .
• the viscosity of the thermosetting resin composition of the present invention is suitable for the mold method from the optimum viscosity range of 1 Pa ⁇ s to 10 Pa ⁇ s suitable for the dispenser method which is a sealing method for LED.
• a wide range of products having a high viscosity range of 10 Pa ⁇ s or more can be provided.
• cured material of 1.5 or more can be provided by using the thermosetting resin composition of this invention.
• thermosetting resin composition is sandwiched between 2 sheets of glass with a Naflon SP packing (4 mm diameter) manufactured by Nichias Co., Ltd.
• the thermosetting resin composition is poured into this, and after degassing under reduced pressure, the temperature is reduced to 80 ° C. For 1 hour, and then by heating at 150 ° C. for 1 hour in order, and the glass was peeled off to obtain a cured product having a smooth 4 mm surface.
• the transmittance at 400 nm was measured with an ultraviolet-visible spectrophotometer UV-1650 manufactured by Shimadzu Corporation.
• the test piece cut the hardened
• the heat resistance test was performed and evaluated by the following method. Two cured products having a thickness of 4 mm were prepared, and the respective light transmittances were measured with an ultraviolet-visible spectrophotometer to obtain initial transmittances. The cured product was placed in an oven at 180 ° C. (constant temperature dryer: DX302 manufactured by Yamato Scientific Co., Ltd.) and heat-treated for a certain time (1000 hours in Table 6).
• ⁇ Heat resistant transparency> The light transmittance of the cured product after the test was measured with a UV-visible spectrophotometer, and the retention at this wavelength (transmittance after heat treatment for a certain time / initial transmittance at each wavelength ⁇ 100) was calculated from the transmittance at 400 nm. And evaluated.
• the retention of light transmittance at 180 ° C. is preferably 90% or more.
• ⁇ Adhesive strength test polyphthalamide resin> The test was conducted according to JIS K6850.
• a test piece was prepared by sandwiching a thermosetting resin composition between a polyphthalamide resin (Amodel (trade name) A-4122NLWH905, manufactured by Solvay Advanced Polymers Co., Ltd.) as a substrate and adjusting the dimensions according to JIS K6850. This was prepared by heat curing at 80 ° C. for 1 hour and then at 150 ° C. for 1 hour.
• the adhesion test was measured using a 5 kN load cell with a tensile and compression tester (Autograph AGS-500B manufactured by Shimadzu Corporation).
• ⁇ Adhesive strength test Ag> The test was conducted according to JIS K6850.
• the test piece is obtained by sandwiching the thermosetting resin composition between silver-plated standard test substrates (manufactured by Nippon Test Panel Co., Ltd.) as a base material, at 80 ° C. for 1 hour, and then at 150 ° C. for 1 hour. It was made by heat curing.
• the adhesion test was measured using a 5 kN load cell with a tensile and compression tester (Autograph AGS-500B manufactured by Shimadzu Corporation).
• ⁇ Heat cycle test> the adhesion test piece prepared by the above method is put in the test area of the thermal shock apparatus TSE-11 manufactured by Espec Co., Ltd., exposed to ⁇ 40 ° C. for 30 minutes, and exposed to 105 ° C. for 30 minutes in one cycle. As shown in FIG. In addition, the movement time between both exposure temperatures was 2 minutes.
• an adhesion test was carried out with a tensile and compression tester, and the adhesion rate retention rate was evaluated based on the decrease rate of the adhesion strength after the heat cycle with respect to the initial adhesion strength measured above.
• thermosetting resin composition is injected with a dispenser into a pre-mold package for a power LED having a thickness of 1.5 mm, a side of 5 mm, an opening of 3.5 mm in diameter, and a bottom of which is silver-plated at 80 ° C. It was heat-cured for 1 hour and then at 150 ° C. for 1 hour. This was put into an electric pressure cooker manufactured by Matsushita Electric Industrial Co., Ltd. and boiled for 59 minutes under a pressurized condition of 98 kPa. Thereafter, the housing was placed in pure water containing red ink and boiled for 1 hour, and adhesion was evaluated by checking whether red ink had entered. If the red ink did not enter, the adhesion was good, and if the red ink entered, the adhesion was poor, and x.
• thermosetting resin composition containing the liquid organosilicon compound is used for sealing an optical semiconductor.
• Table 6 shows tests obtained with cured product 5, cured product 6, cured product 9, cured product 10, cured product 11 and a cured product obtained by curing a commercially available two-part silicone for sealing an LED (Comparative 2). The evaluation result of the heat resistance of a piece is shown.
• cured material obtained using the thermosetting resin composition of this invention has the characteristics of high transparency and a high refractive index, Compared with the conventional phenyl silicone type sealing resin. It was revealed that it was excellent in heat-resistant yellowing. In addition, when the conventional phenyl silicone-based sealing resin is exposed to heat for a long time, the hardness increases and cracks are generated, whereas the thermosetting resin composition of the present invention is used. The obtained cured product was found to have excellent crack resistance with no change in hardness even when exposed to heat for a long time.
• Table 7 shows adhesion of test pieces obtained from cured product 1, cured product 4, cured product 6, cured product 7 and a cured product obtained by curing a commercially available two-part silicone for sealing light-emitting diodes (Comparative 2). The evaluation result of is shown.
• thermosetting resin composition of the present invention was superior in adhesion as compared with conventional phenyl silicone-based sealing resins.
• Table 8 shows the evaluation results of the adhesion rate retention rate after the heat cycle test of the test piece obtained from the cured product 5 and a cured product obtained by curing a commercially available two-part silicone for sealing a light emitting diode (Comparative 2). .
• the cured product obtained using the thermosetting resin composition of the present invention has less decrease in adhesion due to heat shock as compared with the conventional phenyl silicone-based sealing resin. It turned out that it is excellent in long-term reliability as a sealing agent for LED.
• Table 9 shows a composition 5 and a commercially available two-part silicone for sealing a light emitting diode, for a power LED having a thickness of 1.5 mm, a side of 5 mm, an opening of 3.5 mm in diameter, and a bottom of which is silver-plated
• cured with the pre-mold package of is shown.
• the cured product obtained using the thermosetting resin composition of the present invention has no infiltration of red ink even under high-temperature humidification conditions, and maintains adhesion with the LED housing. It turned out that it is excellent in long-term reliability as a sealing agent for LED.
• the cured product obtained using the thermosetting resin composition of the present invention has high transparency and high refractive index characteristics, and is heat resistant compared to conventional phenyl silicone-based sealing resins. It was clarified that it was excellent in yellowing, and excellent in adhesive strength and stress relaxation ability. Moreover, since the cured product of the present invention has a double-decker silsesquioxane skeleton, it can be seen that the cured product is excellent in insulation.
• the cured product of the present invention can be used for optical semiconductor sealing materials, insulating films, sealing agents, adhesives, optical lenses, and the like.

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